Terpenes constitute the largest class of natural products and serve as an important source for medicinal treatments. Despite constant progress in chemical synthesis, the construction of complex polycyclic sesqui- and diterpene scaffolds remains challenging. However, natural cyclase enzymes are able to form the whole variety of terpene structures from just a handful of linear precursors. Man-made catalysts able to mimic such natural enzymes are lacking. Here, we describe examples of sesquiterpene cyclizations inside an enzyme-mimicking supramolecular catalyst. This strategy allowed the formation of the tricyclic sesquiterpene isolongifolene in only four steps. The mechanism of the catalysed cyclization reaction was elucidated using ¹³C-labelling studies and density functional theory calculations.

萜烯是最大的一类天然产物，是药物治疗的重要来源。尽管化学合成不断取得进展，但复杂的多环倍半和二萜支架的构建仍然具有挑战性。然而，天然环化酶能够仅从少数线性前体形成各种萜烯结构。缺乏能够模拟这种天然酶的人造催化剂。在这里，我们描述了酶模拟超分子催化剂内的倍半萜环化的例子。这种策略只需要四个步骤就可以形成三环倍半萜异长叶烯。^使用13 C-标记研究和密度泛函理论计算阐明了催化环化反应的机理。